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CN1227766C - ANonaqueous electrolytic solution and lithium secondary battery - Google Patents

ANonaqueous electrolytic solution and lithium secondary battery Download PDF

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CN1227766C
CN1227766C CNB018171583A CN01817158A CN1227766C CN 1227766 C CN1227766 C CN 1227766C CN B018171583 A CNB018171583 A CN B018171583A CN 01817158 A CN01817158 A CN 01817158A CN 1227766 C CN1227766 C CN 1227766C
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electrolytic solution
lithium secondary
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CN1481593A (en
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浜本俊一
安部浩司
牛越由浩
松森保男
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Ube Corp
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Abstract

作为锂二次电池用非水电解液的非水溶剂，将叔羧酸酯与碳酸亚丙酯和碳酸亚乙酯等环状碳酸酯组合而使用的场合，作为电解质盐，优选使用具有氟原子的锂盐，且该叔羧酸酯，以较少的量、特别是在非水溶剂中占0.5～35重量%的范围左右的量使用为好。As a non-aqueous solvent for a non-aqueous electrolyte solution for lithium secondary batteries, when a tertiary carboxylic acid ester is used in combination with a cyclic carbonate such as propylene carbonate or ethylene carbonate, it is preferable to use a Lithium salt, and the tertiary carboxylic acid ester is preferably used in a small amount, especially in the range of 0.5 to 35% by weight in the non-aqueous solvent.

Description

非水电解液和锂二次电池Non-aqueous electrolyte and lithium secondary battery

【技术领域】【Technical field】

本发明涉及赋予锂二次电池优异电池特性的非水电解液，所说的优异电池特性，是关于电池的循环特性、电容、保存特性等，还涉及使用该非水电解液的锂二次电池。The present invention relates to a non-aqueous electrolytic solution that imparts excellent battery characteristics to a lithium secondary battery. The said excellent battery characteristics refer to the cycle characteristics, capacitance, storage characteristics, etc. of the battery, and also relate to a lithium secondary battery using the non-aqueous electrolytic solution .

【背景技术】【Background technique】

近年来，锂二次电池，作为小型电子机器等的驱动电源，被广泛地使用着。锂二次电池，主要由正极、非水电解液、隔板、和负极构成。特别是，以LiCoO2等的锂复合氧化物作为正极，以碳材料或金属锂作为负极的锂二次电池适合使用。而且，作为这样的锂二次电池用的电解液，碳酸亚乙酯(EC)、碳酸亚丙酯(PC)等环状碳酸酯类适合使用。In recent years, lithium secondary batteries have been widely used as driving power sources for small electronic devices and the like. A lithium secondary battery is mainly composed of a positive electrode, a non-aqueous electrolyte, a separator, and a negative electrode. In particular, a lithium secondary battery having a lithium composite oxide such as LiCoO 2 as a positive electrode and a carbon material or metal lithium as a negative electrode is suitably used. In addition, as the electrolytic solution for such a lithium secondary battery, cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC) are preferably used.

在这样的状况下，特开平7-37613号公报中提出的方案是，作为电解液，通过在一般的非水溶剂(例如，EC、PC)中，组合三氟乙酸甲酯(MTFA)或三甲基乙酸甲酯(MPA)等叔羧酸酯系的非水溶剂来使用，即可作成即使超过4V的电压范围也是稳定的、0℃以下的温度区域的导电性高的、而且，与锂的反应性低、充放电循环寿命长的锂二次电池用电解液。Under such circumstances, the proposal proposed in JP-A-7-37613 is that, as an electrolytic solution, a combination of methyl trifluoroacetate (MTFA) or trifluoroacetate (MTFA) Using a tertiary carboxylate-based non-aqueous solvent such as methyl methyl acetate (MPA), it can be made stable even in the voltage range exceeding 4V, and has high conductivity in the temperature range below 0°C. Moreover, it is compatible with lithium Electrolyte for lithium secondary batteries with low reactivity and long charge-discharge cycle life.

特开平7-37613号公报中记载的具体例是，作为负极，使用玻璃碳，作为非水溶剂，使用PC和MTFA的混合溶剂、EC和MTFA的混合溶剂、或者PC和MPA的混合溶剂。As a specific example described in JP-A-7-37613, glassy carbon is used as the negative electrode, and a mixed solvent of PC and MTFA, a mixed solvent of EC and MTFA, or a mixed solvent of PC and MPA is used as the non-aqueous solvent.

但是，根据本发明人的研究了解到，使用这些混合溶剂作为非水溶剂，作为负极，使用是普通负极材料的天然石墨和人造石墨等碳材料，尤其高结晶化的天然石墨和人造石墨等碳材料的锂二次电池的场合，电解液，在负极分解不可逆容量增大，有时可以看到碳材料发生剥离。该不可逆容量的增大和碳材料的剥离，是由于电解液中的溶剂在充电时分解而发生的，这是起因于碳材料和电解液的界面上的溶剂的电化学还原。尤其了解到，熔点低、介电常数高的PC(碳酸亚丙酯)，在低温下也具有高导电性，但是在使用石墨负极的场合发生PC的分解，则存在锂二次电池用途中不能使用之类的问题。另外还了解到，在EC(碳酸亚乙酯)的场合，在反复充放电间，产生部分分解，发生电池性能的下降。另外也了解到，三甲基乙酸甲酯，沸点是101℃，所以非水溶剂中的三甲基乙酸甲酯的量约达到50重量％以上时，在高温时，电池膨胀、也存在电池性能下降的现象。However, according to the research of the present inventors, it is understood that using these mixed solvents as a non-aqueous solvent, as a negative electrode, use carbon materials such as natural graphite and artificial graphite that are common negative electrode materials, especially highly crystallized carbon such as natural graphite and artificial graphite. In the case of a lithium secondary battery, the electrolyte solution decomposes at the negative electrode and the irreversible capacity increases, and the carbon material may be peeled off in some cases. The increase in the irreversible capacity and the peeling of the carbon material occur due to the decomposition of the solvent in the electrolytic solution during charging, which is caused by the electrochemical reduction of the solvent at the interface between the carbon material and the electrolytic solution. In particular, PC (propylene carbonate), which has a low melting point and a high dielectric constant, has high conductivity even at low temperatures. However, when graphite negative electrodes are used, PC decomposes and cannot be used in lithium secondary batteries. issues such as use. It is also known that, in the case of EC (ethylene carbonate), partial decomposition occurs during repeated charging and discharging, resulting in a decrease in battery performance. It is also known that the boiling point of methyl trimethyl acetate is 101°C, so when the amount of methyl trimethyl acetate in the non-aqueous solvent is about 50% by weight or more, at high temperatures, the battery will expand and the battery performance will also be reduced. decline phenomenon.

另外也了解到，使用上述特开平7-37613号公报中具体记载的LiClO4作为电解液中的电解质盐的场合，在高温下的电池工作中分解发生气体，或对于20℃以上的循环特性容易产生不良影响的问题。In addition, it has also been found that when LiClO 4 specifically described in the above-mentioned JP-A No. 7-37613 is used as the electrolyte salt in the electrolytic solution, gas is decomposed during battery operation at high temperature, or the cycle characteristics at 20° C. or higher are easily Problems with adverse effects.

另一方面，在特开平12-182670号公报中提出，使用含乙酸乙酯、丙酸甲酯、丁酸甲酯等化合物的非水电解液的、可在低温下使用的锂电池。但是，特开平12-182670号公报中提出的非水电池中，虽有低温特性优良之类的特征，但是作为负极例如使用天然石墨和人造石墨等高结晶化的碳材料的锂二次电池的场合，由于金属锂在负极上电析出，所以在电解液中如乙酸乙酯、丙酸甲酯、丁酸甲酯等，在与羰基相邻的碳原子上具有氢原子键合的结构的羧酸酯，有与金属锂反应发生气体、或发生循环特性和保存特性下降的问题。另外，关于丙酸甲酯，由于沸点是79℃，所以在非水溶剂中的含量达到20重量％以上的高温时，具有电池膨胀、电池性能下降的问题。On the other hand, JP-A-12-182670 proposes a lithium battery usable at low temperatures using a non-aqueous electrolytic solution containing compounds such as ethyl acetate, methyl propionate, and methyl butyrate. However, in the non-aqueous battery proposed in Japanese Patent Laid-Open No. 12-182670, although there are characteristics such as excellent low-temperature characteristics, lithium secondary batteries using highly crystalline carbon materials such as natural graphite and artificial graphite as negative electrodes Occasionally, since metal lithium is electro-deposited on the negative electrode, in the electrolyte such as ethyl acetate, methyl propionate, methyl butyrate, etc., the carboxyl with a hydrogen atom-bonded structure on the carbon atom adjacent to the carbonyl group Ester has the problem of generating gas by reacting with lithium metal, or deteriorating cycle characteristics and storage characteristics. In addition, since methyl propionate has a boiling point of 79° C., when the content in the non-aqueous solvent reaches a high temperature of 20% by weight or more, there is a problem of battery swelling and degradation of battery performance.

另外，在特开平9-27328号公报中记载了如下内容，使用含癸酸甲酯和乙酸月桂酯等化合物的非水电解液的非水电池，对于隔板的非水电解液的含浸性优良，电池容量和电池电压大，没有性能偏差。但是，特开平9-27328号公报中记载的非水电池，虽然具有含浸性优异、电池容量和电池电压大的特征，但是作为负极，使用例如天然石墨和人造石墨等的高结晶化的碳材料的锂二次电池的场合，电解液在负极分解不可逆容量增大，有时存在发生碳材料的剥离现象。该不可逆容量的增大或碳材料的剥离，是由于电解液中的溶剂在充电时分解引起的，并且是起因于碳材料与电解液的界面上的溶剂的电化学还原。特别是，像癸酸甲酯和乙酸月桂酯等，与羰基邻接的碳原子具有氢原子键合结构的羧酸酯的场合，在低温下也显示高导电性，但是使用石墨负极的场合，在反复充放电间，发生部分羧酸酯的分解，故有发生循环特性下降的问题。In addition, JP-A-9-27328 discloses that a non-aqueous battery using a non-aqueous electrolyte containing compounds such as methyl caprate and lauryl acetate has excellent impregnation properties of the separator with the non-aqueous electrolyte. , large battery capacity and battery voltage, no performance deviation. However, the non-aqueous battery described in JP-A-9-27328 has excellent impregnation properties, high battery capacity and high battery voltage, but as the negative electrode, highly crystalline carbon materials such as natural graphite and artificial graphite are used. In the case of a lithium secondary battery, the electrolytic solution decomposes at the negative electrode to increase the irreversible capacity, and sometimes there is a phenomenon of peeling off of the carbon material. This increase in irreversible capacity or peeling off of the carbon material is caused by the decomposition of the solvent in the electrolytic solution during charging, and is caused by the electrochemical reduction of the solvent at the interface between the carbon material and the electrolytic solution. In particular, like methyl caprate and lauryl acetate, etc., when the carbon atom adjacent to the carbonyl group has a hydrogen atom bonding structure, it shows high conductivity at low temperature, but when using a graphite negative electrode, the During repeated charging and discharging, a part of the carboxylic acid ester is decomposed, so there is a problem that the cycle characteristics are degraded.

【发明的内容】【Content of invention】

本发明的目的在于，解决有关上述以往公知的锂二次电池用电解液的课题，提供一种电池循环特性优异，进而电容和充电状态下的保存特性等电池特性也优异的、可控制高温使用时的电池膨胀的锂二次电池，以及适用于锂二次电池的非水电解液。The object of the present invention is to solve the above-mentioned problems related to the conventionally known electrolyte solution for lithium secondary batteries, and to provide a battery that is excellent in cycle characteristics, and also has excellent battery characteristics such as capacity and storage characteristics in a charged state, and can be used at a controlled high temperature. A lithium secondary battery that expands when the battery is used, and a non-aqueous electrolyte suitable for the lithium secondary battery.

通过本发明人的研究弄清楚了如下事实，作为锂二次电池用非水电解液的非水溶剂，将如上述特开平7-37613号公报中记载的叔羧酸酯与碳酸亚丙酯和碳酸亚乙酯等环状碳酸酯组合使用的场合，作为电解质盐，优选使用有氟原子的锂盐，而且该叔羧酸酯，量较少，特别优选的用量是，在非水溶剂中约占0.5～35重量％范围的量。Through the research of the present inventors, the following facts have been clarified. As the non-aqueous solvent of the non-aqueous electrolytic solution for lithium secondary batteries, the tertiary carboxylate, propylene carbonate and When cyclic carbonates such as ethylene carbonate are used in combination, as the electrolyte salt, lithium salts with fluorine atoms are preferably used, and the amount of the tertiary carboxylic acid ester is relatively small, and the particularly preferred amount is about An amount in the range of 0.5 to 35% by weight.

本发明人进一步发现，在该酯的醇残基是碳原子数4以上的烷基的场合，该叔羧酸酯，与由聚丙烯和聚乙烯等聚烯烃材料构成的隔板的亲合性高，因此，可以有利地用作锂二次电池用非水溶剂的构成成分。The present inventors further found that when the alcohol residue of the ester is an alkyl group with 4 or more carbon atoms, the affinity of the tertiary carboxylate with a separator made of polyolefin materials such as polypropylene and polyethylene Therefore, it can be advantageously used as a constituent of a non-aqueous solvent for a lithium secondary battery.

因此，本发明提供一种锂二次电池，其特征在于，该电池是备有，由含锂复合氧化物的材料构成的正极、由含碳的材料构成的负极、隔板、和电解质盐溶于非水溶剂中构成的非水电解液的锂二次电池，该电解质盐是有氟原子的锂盐，该非水溶剂含环状碳酸酯，而且该非水溶剂中还含有0.5～35重量％含量的用下述通式(I)：Therefore, the present invention provides a lithium secondary battery characterized in that the battery is equipped with a positive electrode made of a lithium-containing composite oxide material, a negative electrode made of a carbon-containing material, a separator, and an electrolyte salt solution. A lithium secondary battery with a non-aqueous electrolyte solution formed in a non-aqueous solvent, the electrolyte salt is a lithium salt with fluorine atoms, the non-aqueous solvent contains a cyclic carbonate, and the non-aqueous solvent also contains 0.5 to 35 wt. % content with the following general formula (I):

表示的叔羧酸酯(式中，R1、R2、和R3，分别独立地，表示甲基、乙基、氟原子、或氯原子，而且R4表示碳原子数1～20的烃基)。The tertiary carboxylic acid ester represented (wherein, R 1 , R 2 , and R 3 independently represent a methyl group, an ethyl group, a fluorine atom, or a chlorine atom, and R 4 represents a hydrocarbon group with 1 to 20 carbon atoms ).

本发明提供一种锂二次电池，其特征在于，该电池是备有，由含锂复合氧化物的材料构成的正极、由含碳的材料构成的负极、隔板、和电解质盐溶于非水溶剂中构成的非水电解液的锂二次电池，该电解质盐是有氟原子的锂盐，该非水溶剂含环状碳酸酯，而且该非水溶剂中还含有0.5重量％以上含量的用上述通式(I)表示的叔羧酸酯(但是，式中，R1、R2、和R3，分别独立地，表示甲基、乙基、氟原子、或氯原子，R4，表示碳原子数4～20的烃基)。The present invention provides a lithium secondary battery, which is characterized in that the battery is equipped with a positive electrode composed of a lithium-containing composite oxide material, a negative electrode composed of a carbon-containing material, a separator, and an electrolyte salt dissolved in a non- A lithium secondary battery of a non-aqueous electrolyte solution formed in an aqueous solvent, the electrolyte salt is a lithium salt having fluorine atoms, the non-aqueous solvent contains a cyclic carbonate, and the non-aqueous solvent also contains 0.5% by weight or more of Tertiary carboxylic acid esters represented by the above general formula (I) (however, in the formula, R 1 , R 2 , and R 3 each independently represent a methyl group, an ethyl group, a fluorine atom, or a chlorine atom, and R 4 , represents a hydrocarbon group having 4 to 20 carbon atoms).

本发明还提供一种锂二次电池用非水电解液，其特征在于，该电解液是含氟原子的锂盐作为电解质盐溶于含环状碳酸酯的非水溶剂中构成的非水电解液，该非水溶剂还含有0.5～35重量％含量的用上述通式(I)表示的叔羧酸酯(式中，R1、R2、R3，分别独立地，表示甲基、乙基、氟原子、或氯原子，而R4，表示碳原子数1～20的烃基)。The present invention also provides a non-aqueous electrolytic solution for lithium secondary batteries, which is characterized in that the electrolytic solution is a non-aqueous electrolytic solution formed by dissolving a lithium salt containing fluorine atoms in a non-aqueous solvent containing a cyclic carbonate as an electrolyte salt. liquid, the non-aqueous solvent also contains 0.5 to 35% by weight of the tertiary carboxylic acid ester represented by the above general formula (I) (wherein, R 1 , R 2 , and R 3 independently represent methyl, ethyl, and group, fluorine atom, or chlorine atom, and R 4 represents a hydrocarbon group having 1 to 20 carbon atoms).

本发明还提供一种锂二次电池用非水电解液，其特征在于，该电解液是含氟原子的锂盐作为电解质盐溶于含环状碳酸酯的非水溶剂中构成的非水电解液，该非水溶剂还含有0.5重量％以上含量的用上述通式(I)表示的叔羧酸酯(但是，式中R1、R2和R3，分别独立地，表示甲基、乙基、氟原子、或氯原子，R4，表示碳原子数4～20，优选4～12、特别优选4～8的烃基)。The present invention also provides a non-aqueous electrolytic solution for lithium secondary batteries, which is characterized in that the electrolytic solution is a non-aqueous electrolytic solution formed by dissolving a lithium salt containing fluorine atoms in a non-aqueous solvent containing a cyclic carbonate as an electrolyte salt. liquid, the non-aqueous solvent also contains 0.5% by weight or more of the tertiary carboxylic acid ester represented by the above general formula (I) (however, in the formula, R 1 , R 2 and R 3 independently represent methyl, ethyl group, fluorine atom, or chlorine atom, R 4 represents a hydrocarbon group having 4 to 20 carbon atoms, preferably 4 to 12, particularly preferably 4 to 8 carbon atoms).

【发明的详细说明】[Detailed description of the invention]

在向将电解质盐溶于非水溶剂的电解液中导入的用上述通式(I)表示的叔羧酸酯中，优选R1、R2和R3，分别独立地，表示甲基或乙基。R4，优选的是像甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一(烷)基、十二(烷)基、十三(烷)基、十四(烷)基、十五(烷)基、十六(烷)基、十七(烷)基、十八(烷)基、还有二十(烷)基(エイコサニル基)那样的碳原子数1～20的烷基。烷基，像异丙基、异丁基、异戊基、异丁基、仲丁基、叔丁基、异辛基、仲辛基、2-乙基己基、异壬基、异癸基、异十八(烷)基那样的支链烷基也可以。另外，像乙烯基、烯丙基、炔丙基那样的不饱和烃基、苯基、甲苯基、联苯基那样的芳基或苄基也可以。Among the tertiary carboxylic acid esters represented by the above general formula (I) introduced into the electrolytic solution in which the electrolyte salt is dissolved in a non-aqueous solvent, it is preferable that R 1 , R 2 and R 3 each independently represent methyl or ethyl base. R 4 is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and eicosyl An alkyl group having 1 to 20 carbon atoms such as (Eikosanyl group). Alkyl, like isopropyl, isobutyl, isopentyl, isobutyl, sec-butyl, tert-butyl, isooctyl, sec-octyl, 2-ethylhexyl, isononyl, isodecyl, A branched chain alkyl group such as isocetadecyl group may also be used. In addition, unsaturated hydrocarbon groups such as vinyl, allyl, and propargyl, aryl groups such as phenyl, tolyl, and biphenyl, or benzyl groups may also be used.

作为通式(I)的叔羧酸酯的具体例，可举出，例如，三甲基乙酸甲酯(R1＝R2＝R3＝R4＝甲基)、三甲基乙酸乙酯(R1＝R2＝R3＝甲基、R4＝乙基)、三甲基乙酸丙酯(R1＝R2＝R3＝甲基、R4＝正丙基)、三甲基乙酸异丙酯(R1＝R2＝R3＝甲基、R4＝异丙基)、三甲基乙酸丁酯(R1＝R2＝R3＝甲基、R4＝正丁基)、三甲基乙酸仲丁酯(R1＝R2＝R3＝甲基、R4＝仲丁基)、三甲基乙酸异丁酯(R1＝R2＝R3＝甲基、R4＝异丁基)、三甲基乙酸叔丁酯(R1＝R2＝R3＝甲基、R4＝叔丁基)、三甲基乙酸辛酯(R1＝R2＝R3＝甲基、R4＝正辛基)、三甲基乙酸仲辛酯(R1＝R2＝R3＝甲基、R4＝仲辛基)、三甲基乙酸壬酯(R1＝R2＝R3＝甲基、R4＝正壬基)、三甲基乙酸癸酯(R1＝R2＝R3＝甲基、R4＝正癸基)、三甲基乙酸十一(烷)基酯(R1＝R2＝R3＝甲基、R4＝正十一(烷)基)、三甲基乙酸月桂酯(R1＝R2＝R3＝甲基、R4＝正月桂基)、三甲基乙酸乙烯酯(R1＝R2＝R3＝甲基、R4＝乙烯基)、三甲基乙酸烯丙酯(R1＝R2＝R3＝甲基、R4＝烯丙基)、三甲基乙酸炔丙酯(R1＝R2＝R3＝甲基、R4＝炔丙基)、三甲基乙酸苯酯(R1＝R2＝R3＝甲基、R4＝苯基)、三甲基乙酸对甲苯酯(R1＝R2＝R3＝甲基、R4＝对甲苯基)、三甲基乙酸联苯酯(R1＝R2＝R3＝甲基、R4＝联苯基)、三甲基乙酸苄酯(R1＝R2＝R3＝甲基、R4＝苄基)、2，2-二甲基丁酸甲酯(R1＝R2＝R4＝甲基、R3＝乙基)、2-乙基-2-甲基丁酸甲酯(R1＝R4＝甲基、R2＝R3＝乙基)、2，2-二乙基丁酸甲酯(R1＝R2＝R3＝乙基、R4＝甲基)等，但是，本发明中使用的叔羧酸酯，并不限定于上述的具体化合物，从本发明的宗旨可以容易类推的各种组合都是可能的。Specific examples of tertiary carboxylic acid esters of the general formula (I) include, for example, methyl trimethyl acetate (R 1 =R 2 =R 3 =R 4 =methyl), ethyl trimethyl acetate (R 1 =R 2 =R 3 =methyl, R 4 =ethyl), trimethylpropyl acetate (R 1 =R 2 =R 3 =methyl, R 4 =n-propyl), trimethyl Isopropyl acetate (R 1 = R 2 = R 3 = methyl, R 4 = isopropyl), trimethylbutyl acetate (R 1 = R 2 = R 3 = methyl, R 4 = n-butyl ), sec-butyl trimethylacetate (R 1 =R 2 =R 3 =methyl, R 4 =sec-butyl), isobutyl trimethylacetate (R 1 =R 2 =R 3 =methyl, R 4 =isobutyl), tert-butyl trimethylacetate (R 1 =R 2 =R 3 =methyl, R 4 =tert-butyl), octyl trimethylacetate (R 1 =R 2 =R 3 = methyl, R 4 = n-octyl), sec-octyl trimethylacetate (R 1 = R 2 = R 3 = methyl, R 4 = sec-octyl), nonyl trimethylacetate (R 1 =R 2 =R 3 =methyl, R 4 =n-nonyl), decyl trimethylacetate (R 1 =R 2 =R 3 =methyl, R 4 =n-decyl), decyl trimethylacetate Mono(alkyl)yl esters (R 1 =R 2 =R 3 =methyl, R 4 =n-undecyl), trimethyllauryl acetate (R 1 =R 2 =R 3 =methyl, R 4 =n-lauryl), trimethylvinyl acetate (R 1 =R 2 =R 3 =methyl, R 4 =vinyl), allyl trimethylacetate (R 1 =R 2 =R 3 = methyl, R 4 = allyl), propargyl trimethylacetate (R 1 = R 2 = R 3 = methyl, R 4 = propargyl), phenyl trimethylacetate (R 1 = R 2 =R 3 =methyl, R 4 =phenyl), p-cresyl trimethylacetate (R 1 =R 2 =R 3 =methyl, R 4 =p-tolyl), biphenyl trimethylacetate ester (R 1 =R 2 =R 3 =methyl, R 4 =biphenyl), benzyl trimethylacetate (R 1 =R 2 =R 3 =methyl, R 4 =benzyl), 2, Methyl 2-dimethylbutyrate (R 1 =R 2 =R 4 =methyl, R 3 =ethyl), methyl 2-ethyl-2-methylbutyrate (R 1 =R 4 =methyl group, R 2 =R 3 =ethyl), methyl 2,2-diethylbutyrate (R 1 =R 2 =R 3 =ethyl, R 4 =methyl), etc. However, the present invention uses The tertiary carboxylic acid esters are not limited to the specific compounds mentioned above, and various combinations that can be easily deduced from the gist of the present invention are possible.

用通式(I)表示的叔羧酸酯，如上所述，在电解液中含量过多时，存在电解液的传导率等改变、电池性能下降的问题。另外，过少时，得不到所期待的电池性能，所以在非水溶剂中的含量，是0.5～35重量％的范围，特别优选的是1～20重量％的范围。When the tertiary carboxylic acid ester represented by the general formula (I) is contained too much in the electrolytic solution as described above, there is a problem that the conductivity of the electrolytic solution, etc. changes, and the performance of the battery decreases. Also, if it is too small, the expected battery performance cannot be obtained, so the content in the non-aqueous solvent is in the range of 0.5 to 35% by weight, particularly preferably in the range of 1 to 20% by weight.

本发明的非水溶剂，是以叔羧酸酯和环状碳酸酯作为必要构成成分。而且，也优选加入链状碳酸酯。The non-aqueous solvent of the present invention contains tertiary carboxylic acid ester and cyclic carbonate as essential constituents. Furthermore, it is also preferable to add a chain carbonate.

作为环状碳酸酯，可以优选举出碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸亚乙烯酯(VC)。这些环状碳酸酯，可以使用1种，还可以2种以上组合使用。Examples of the cyclic carbonate preferably include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC). These cyclic carbonates may be used alone or in combination of two or more.

作为链状碳酸酯，可以优选举出碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸乙基·甲基酯(EMC)、碳酸甲基·丙基酯(MPC)、碳酸异丙基·甲基酯(IPMC)、碳酸丁基·甲基酯(BMC)、碳酸异丁基·甲基酯(IBMC)、碳酸仲丁基·甲基酯(SBMC)、碳酸叔丁基·甲基酯(TBMC)。这些链状碳酸酯可以使用1种，也可以2种以上组合使用。As chain carbonates, preferably dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), diethyl carbonate Propyl methyl carbonate (IPMC), butyl methyl carbonate (BMC), isobutyl methyl carbonate (IBMC), sec-butyl methyl carbonate (SBMC), tert-butyl carbonate methyl ester (TBMC). These chain carbonates may be used alone or in combination of two or more.

环状碳酸酯和链状碳酸酯可以分别任意地选择，可以将这些任意地组合使用。非水溶剂中环状碳酸酯的含量，优选为10～80重量％范围的量。在并用链状碳酸酯的场合，该非水溶剂中的含量，优选为80重量％以下的量。Cyclic carbonates and chain carbonates can be selected arbitrarily, respectively, and can be used in any combination. The content of the cyclic carbonate in the non-aqueous solvent is preferably in an amount in the range of 10 to 80% by weight. When a chain carbonate is used in combination, the content in the non-aqueous solvent is preferably 80% by weight or less.

而且，本发明的非水溶剂还可以含有环状酯。作为环状酯，可以优选举出γ-丁内酯(GBL)、还有γ-戊内酯(GVL)。环状酯，可以使用1种，也可以2种以上组合使用。非水溶剂中含有环状酯的场合，优选其含量为70重量％以下，特别优选为30～70重量％范围的量。再者，环状酯着火点高，因此将其含在电解液的非水溶剂中时，还可以提供安全性优良的锂二次电池。Furthermore, the non-aqueous solvent of the present invention may contain a cyclic ester. As a cyclic ester, gamma-butyrolactone (GBL) and gamma-valerolactone (GVL) are mentioned preferably. Cyclic esters may be used alone or in combination of two or more. When the cyclic ester is contained in the non-aqueous solvent, its content is preferably 70% by weight or less, particularly preferably 30 to 70% by weight. Furthermore, since the cyclic ester has a high ignition point, when it is contained in the non-aqueous solvent of the electrolytic solution, a lithium secondary battery excellent in safety can also be provided.

作为导入到本发明电解液中的电解质盐，可以使用含氟原子的锂盐。作为合适的含氟原子的锂盐的例子，可以举出，LiPF6、LiBF4、LiAsF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiPF4(CF3)2、LiPF3(C2F5)3、LiPF3(CF3)3、LiPF3(iso-C3F7)3、LiPF5(iso-C3F7)等。这些电解质盐，可以使用1种，也可以2种以上组合使用。这些电解质盐，可溶于上述非水溶剂中，通常按0.1～3M，优选按0.5～2M的浓度使用。As the electrolyte salt introduced into the electrolytic solution of the present invention, a lithium salt containing fluorine atoms can be used. Examples of suitable lithium salts containing fluorine atoms include LiPF 6 , LiBF 4 , LiAsF 6 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiPF 3 (iso-C 3 F 7 ) 3 , LiPF 5 (iso-C 3 F 7 ) etc. These electrolyte salts may be used alone or in combination of two or more. These electrolyte salts are soluble in the above-mentioned non-aqueous solvent, and are usually used at a concentration of 0.1-3M, preferably 0.5-2M.

本发明的电解液，例如，可以通过混合上述环状碳酸酯和链状碳酸酯，根据需要再混合环状酯，然后向其中溶解通式(I)的叔羧酸酯，再向其中溶解作为上述含氟的锂盐的电解质盐得到的。The electrolytic solution of the present invention, for example, can be by mixing above-mentioned cyclic carbonate and chain carbonate, and then mixes cyclic ester as required, then dissolves the tertiary carboxylic acid ester of general formula (I) thereinto, then dissolves thereinto as The electrolyte salt of the above-mentioned fluorine-containing lithium salt is obtained.

本发明的电解液，作为锂二次电池的构成材料可有利地使用。The electrolytic solution of the present invention can be advantageously used as a constituent material of a lithium secondary battery.

作为本发明的锂二次电池的正极，可使用含锂复合氧化物的材料。作为正极材料(正极活性物质)，例如，可以使用选自钴、锰、镍、铬、铁和钒中的至少1种金属与锂的复合金属氧化物。作为这样的复合金属氧化物的具体例，可以举出，LiCoO2、LiMn2O4、和LiNiO2等，还可以是钴与混合了锰的锂的复合金属氧化物，钴与混合了镍的锂的复合金属氧化物。As the positive electrode of the lithium secondary battery of the present invention, a lithium-containing composite oxide material can be used. As the positive electrode material (positive electrode active material), for example, a composite metal oxide of at least one metal selected from cobalt, manganese, nickel, chromium, iron, and vanadium and lithium can be used. Specific examples of such composite metal oxides include LiCoO 2 , LiMn 2 O 4 , and LiNiO 2 , etc., and composite metal oxides of cobalt and lithium mixed with manganese, cobalt and lithium mixed with nickel, etc. Lithium composite metal oxide.

正极，是通过将上述正极材料，和将乙炔黑、炭黑等的导电剂，与聚四氟乙烯(PTFE)、聚偏氟乙烯(PVDF)、苯乙烯与丁二烯的共聚物(SBR)、丙烯腈与丁二烯的共聚物(NBR)、羧甲基纤维素(CMC)等粘合剂混炼制成正极合剂后，将该正极材料涂覆到作为集电体的铝或不锈钢制的箔或板条上，干燥、加压成型后，在50℃～250℃左右的温度下和真空下加热处理2小时左右制作的。The positive electrode is made by using the above-mentioned positive electrode material, and conductive agents such as acetylene black and carbon black, and polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene and butadiene copolymer (SBR) , acrylonitrile and butadiene copolymer (NBR), carboxymethyl cellulose (CMC) and other binders are mixed to make a positive electrode mixture, and the positive electrode material is coated on aluminum or stainless steel as a collector. It is made of foil or lath, dried and press-molded, and then heat-treated at a temperature of about 50°C to 250°C and under vacuum for about 2 hours.

作为负极活性物质，可使用具有能进行吸留、放出锂的石墨型晶体结构的碳材料[热分解碳类、焦炭类、石墨类(人造石墨、天然石墨等)、有机高分子化合物燃烧体、碳纤维]。特别优选使用，具有晶面(002)的面间距(d002)是0.335～0.340nm(纳米)的石墨型晶体结构的碳材料。再者，像碳材料那样的粉末材料与乙烯-丙烯-双烯三元共聚物(EPDM)、聚四氟乙烯(PTFE)、聚偏氟乙烯(PVDF)、苯乙烯和丁二烯的共聚物(SBR)、丙烯腈与丁二烯的共聚物(NBR)、羧甲基纤维素(CMC)等粘合剂混炼制成负极合剂使用。As the negative electrode active material, a carbon material having a graphite-type crystal structure capable of occluding and releasing lithium [pyrolytic carbon, coke, graphite (artificial graphite, natural graphite, etc.), organic polymer compound combustion body, carbon fiber]. In particular, a carbon material having a graphite-type crystal structure with a crystal plane (002) whose interplanar distance (d002) is 0.335 to 0.340 nm (nanometer) is preferably used. Furthermore, powder materials such as carbon materials and copolymers of ethylene-propylene-diene terpolymer (EPDM), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene and butadiene (SBR), copolymer of acrylonitrile and butadiene (NBR), carboxymethyl cellulose (CMC) and other binders are mixed to make negative electrode mixture.

作为隔板，优选使用由多微孔膜构成的隔板，所说的多微孔膜是由聚丙烯和聚乙烯等聚烯烃材料形成的，但是也可以使用由其它材料形成的隔板(例如，织物、无纺织物)。As the separator, it is preferable to use a separator composed of a microporous film formed of polyolefin materials such as polypropylene and polyethylene, but it is also possible to use a separator formed of other materials (such as , fabrics, non-woven fabrics).

本发明的锂二次电池的结构，没有特别地限定，可以举出，具有正极、负极、和单层或多层隔板的硬币型电池，另外，具有正极、负极和卷状隔板的圆筒型电池和方型电池等。The structure of the lithium secondary battery of the present invention is not particularly limited, and can include a coin-type battery with a positive electrode, a negative electrode, and a single-layer or multilayer separator, and a round battery with a positive electrode, a negative electrode, and a roll-shaped separator. Cylindrical batteries and square batteries, etc.

下面，示出实施例和比较例。Next, examples and comparative examples are shown.

[实施例1][Example 1]

[电解液的配制][Preparation of Electrolyte]

配制EC(碳酸亚乙酯)∶DEC(碳酸二乙酯)∶三甲基乙酸甲酯[上述式(I)中R1＝R2＝R3＝R4＝甲基，重量比＝30∶60∶10]的非水溶剂，然后向其中溶解LiPF6并使其达到1M的浓度，配制电解液。Preparation of EC (ethylene carbonate): DEC (diethyl carbonate): methyl trimethyl acetate [R 1 = R 2 = R 3 = R 4 = methyl in the above formula (I), weight ratio = 30: 60:10] in a non-aqueous solvent, and then dissolve LiPF 6 therein to a concentration of 1M to prepare an electrolyte.

[锂二次电池的制作和电池特性的测定][Production of Lithium Secondary Battery and Measurement of Battery Characteristics]

将LiCoO2(正极活性物质)80重量％、乙炔黑(导电剂)10重量％、聚偏氟乙烯(粘合剂)10重量％进行混合，再向其中添加1-甲基-2吡咯烷酮制成淤浆状涂覆到铝箔上。然后，将其干燥、加压成型制成正极。将天然石墨(负极活性物质)90重量％、聚偏氟乙烯(粘合剂)10重量％进行混合，再向其中添加1-甲基-2吡咯烷酮制成淤浆状涂覆到铜箔上。然后，将其干燥、加压成型、加热处理制成负极。而且，使用聚丙烯多微孔性膜的隔板，注入上述电解液制作出硬币电池(直径20mm，厚度3.2mm)。80% by weight of LiCoO 2 (positive electrode active material), 10% by weight of acetylene black (conductive agent), and 10% by weight of polyvinylidene fluoride (binder) were mixed, and 1-methyl-2-pyrrolidone was added to it. Slurry coated onto aluminum foil. Then, it is dried and press-molded to make a positive electrode. 90% by weight of natural graphite (negative electrode active material) and 10% by weight of polyvinylidene fluoride (binder) were mixed, and 1-methyl-2-pyrrolidone was added thereto to form a slurry and coated on copper foil. Then, it is dried, press-molded, and heat-treated to make a negative electrode. Furthermore, a separator of a polypropylene microporous membrane was injected with the above electrolytic solution to produce a coin battery (diameter: 20 mm, thickness: 3.2 mm).

使用该硬币电池，在室温(20℃)下，0.8mA的恒电流恒电压下，充电5小时到终止电压4.2V，接着，在0.8mA的恒电流下，放电到终止电压2.7V，反复进行该充放电。初期充放电容量，与使用1M的LiPF6+EC∶DEC(重量比)＝30∶70作为电解液(无添加剂)的场合(比较例3)大致是等同的，测定50循环后的电池特性时，将初期放电容量定为100％时的放电容量维持率是90.7％。另外，低温和高温工作时的诸特性也良好。硬币电池的制作条件和电池特性示于表1中。Using this coin cell, at room temperature (20°C), charge at a constant current of 0.8mA and a constant voltage for 5 hours to a cut-off voltage of 4.2V, then discharge at a constant current of 0.8mA to a cut-off voltage of 2.7V, and repeat The charge and discharge. The initial charge-discharge capacity is approximately the same as the case where 1M LiPF 6 +EC:DEC (weight ratio) = 30:70 was used as the electrolyte solution (without additives) (Comparative Example 3), and the battery characteristics after 50 cycles were measured , the discharge capacity maintenance rate was 90.7% when the initial discharge capacity was defined as 100%. In addition, various characteristics at low temperature and high temperature operation are also good. Table 1 shows the production conditions and battery characteristics of the coin cell.

[实施例2～11][Embodiments 2-11]

除将硬币电池的制作条件改变成表1中记载的那样以外，其余与实施例1相同地制作硬币电池，并测定50循环后的放电容量维持率。其测定结果示于表1中。A coin cell was produced in the same manner as in Example 1 except that the production conditions of the coin cell were changed to those described in Table 1, and the discharge capacity retention rate after 50 cycles was measured. The measurement results are shown in Table 1.

[比较例1～5][Comparative examples 1 to 5]

除将硬币电池的制作条件改变成表1中记载的那样以外，其余与实施例1相同地制作硬币电池，并测定50循环后的放电容量维持率。其测定结果示于表1中。A coin cell was produced in the same manner as in Example 1 except that the production conditions of the coin cell were changed to those described in Table 1, and the discharge capacity retention rate after 50 cycles was measured. The measurement results are shown in Table 1.

[实施例12][Example 12]

除了配制EC∶PC(碳酸亚丙酯)∶DEC∶三甲基乙酸辛酯(重量比)＝35∶35∶25∶5的非水溶剂，并将负极作成焦炭的以外，其余与实施例1同样地制作硬币电池。测定该硬币电池的50循环后的放电容量维持率时，初期放电容量定为100％时的放电容量维持率是86.5％。硬币电池的制作条件和电池特性示于表1中。Except preparation EC: PC (propylene carbonate): DEC: the nonaqueous solvent of trimethyl octyl acetate (weight ratio)=35: 35: 25: 5, and negative electrode is made coke, all the other and embodiment 1 Make a coin battery in the same way. When the discharge capacity retention rate after 50 cycles of this coin battery was measured, the discharge capacity retention rate when the initial discharge capacity was 100% was 86.5%. Table 1 shows the production conditions and battery characteristics of the coin cell.

[比较例6][Comparative Example 6]

除了配制EC∶PC∶辛酸甲酯(重量比)＝49∶49∶2的非水溶剂使用以外，其余与实施例12同样地制作硬币电池。测定该硬币电池的50循环的放电容量维持率时，将初期放电容量定为100％时的放电容量维持率是71.3％。硬币电池的制作条件和电池特性示于表1中。A coin battery was fabricated in the same manner as in Example 12, except that a non-aqueous solvent of EC:PC:octylic acid methyl ester (weight ratio) = 49:49:2 was prepared and used. When the discharge capacity retention rate of this coin battery was measured for 50 cycles, the discharge capacity retention rate when the initial discharge capacity was defined as 100% was 71.3%. Table 1 shows the production conditions and battery characteristics of the coin cell.

[实施例13][Example 13]

配制EC∶GBL(γ-丁内酯)∶IBMC(碳酸异丁基·甲基酯)∶三甲基乙酸辛酯(重量比)＝25∶50∶20∶5的非水溶剂，再向其中溶解LiBF4并使其达到1.2M的浓度，制备非水电解液。使用该非水电解液，作为正极使用LiMn2O4，除此之外，其余与实施例1同样地制作硬币电池。测定该硬币电池的50循环后的放电容量维持率时，将初期放电容量定为100％时的放电容量维持率是83.4％。该硬币电池的制作条件和电池特性示于表1中。Prepare EC: GBL (γ-butyrolactone): IBMC (isobutyl methyl carbonate): octyl trimethylacetate (weight ratio) = 25: 50: 20: 5 non-aqueous solvent, and then add Dissolve LiBF4 and bring it to a concentration of 1.2M to prepare a non-aqueous electrolyte. A coin battery was fabricated in the same manner as in Example 1 except that this non-aqueous electrolytic solution was used and LiMn 2 O 4 was used as the positive electrode. When the discharge capacity retention rate after 50 cycles of this coin battery was measured, the discharge capacity retention rate when the initial discharge capacity was 100% was 83.4%. Table 1 shows the production conditions and battery characteristics of this coin battery.

[实施例14][Example 14]

除了配制EC∶GBL∶IBMC∶三甲基乙酸癸酯(重量比)＝25∶50∶20∶5的非水溶剂使用之外，其余与实施例13同样地制作硬币电池。测定该硬币电池的50循环后的放电容量维持率时，将初期放电容量定为100％时的放电容量维持率是82.1％。该硬币电池的制作条件和电池特性示于表1中。A coin cell was produced in the same manner as in Example 13, except that a non-aqueous solvent of EC:GBL:IBMC:decyl trimethylacetate (weight ratio) = 25:50:20:5 was prepared and used. When the discharge capacity retention rate after 50 cycles of this coin battery was measured, the discharge capacity retention rate when the initial discharge capacity was 100% was 82.1%. Table 1 shows the production conditions and battery characteristics of this coin battery.

[实施例15][Example 15]

除了配制EC∶GBL∶IBMC∶三甲基乙酸月桂酯(重量比)＝25∶50∶20∶5的非水溶剂使用之外，其余与实施例13同样地制作硬币电池。测定该硬币电池的50循环后的放电容量维持率时，将初期放电容量定为100％时的放电容量维持率是81.7％。该硬币电池的制作条件和电池特性示于表1中。A coin cell was fabricated in the same manner as in Example 13, except that a non-aqueous solvent of EC:GBL:IBMC:trimethyllauryl acetate (weight ratio) = 25:50:20:5 was prepared and used. When the discharge capacity retention rate after 50 cycles of this coin battery was measured, the discharge capacity retention rate when the initial discharge capacity was 100% was 81.7%. Table 1 shows the production conditions and battery characteristics of this coin battery.

[比较例7][Comparative Example 7]

除配制EC∶GBL(重量比)＝30∶70的非水溶剂使用之外，其余与实施例13同样地制作硬币电池。测定该硬币电池的50循环后的放电容量维持率时，将初期放电容量定为100％时的放电容量维持率是67.4％。该硬币电池的制作条件和电池特性示于表1中。A coin cell was fabricated in the same manner as in Example 13, except that a non-aqueous solvent of EC:GBL (weight ratio) = 30:70 was used. When the discharge capacity retention rate after 50 cycles of this coin battery was measured, the discharge capacity retention rate when the initial discharge capacity was 100% was 67.4%. Table 1 shows the production conditions and battery characteristics of this coin battery.

表1 正极 负极 Li盐(M) 环状碳酸酯或环状酯(重量％) 链状碳酸酯(重量％) 叔羧酸酯或其它的酯(重量％) 50循环放电容量维持率％   实施例1 LiCoO2   人造石墨   LiPF61M   EC30   DEC60   三甲基乙酸甲酯10 90.7   实施例2 LiCoO2   人造石墨   LiPF61M   EC30   DEC50   三甲基乙酸甲酯20 91.8   实施例3 LiCoO2   人造石墨   LiPF61M   EC30   DEC40   三甲基乙酸甲酯30 91.4   实施例4 LiCoO2   人造石墨   LiPF61M   EC30   DEC30   三甲基乙酸甲酯40 85.9   比较例1 LiCoO2   人造石墨   LiClO41M   EC50 无   三甲基乙酸甲酯50 65.5   比较例2 LiCoO2   人造石墨   LiCIO41M   PC50 无   三甲基乙酸甲酯50 未充放电   比较例3 LiCoO2   人造石墨   LiPF61M   EC30   DEC70 无 81.7   实施例5 LiCoO2   人造石墨   LiPF61M   EC/PC30/5   DEC50   三甲基乙酸乙酯15 91.6   实施例6 LiCoO2   人造石墨   LiPF61M   EC/PC/VC27/5/3   DMC/EMC15/40   三甲基乙酸甲酯10 92.1 实施例7 LiCoO2 人造石墨 LiPF61M EC/PC/VC27/5/3   DMC/IPMC15/40 三甲基乙酸甲酯10 91.9   实施例8 LiMn2O4   人造石墨   LiPF61M   EC/PC30/5   DEC50   三甲基乙酸甲酯15 92.1   比较例4 LiCoO2   人造石墨   LiPF61M   EC/VC15/5   DMC23   乙酸乙酯57 81.1   实施例9 LiCoO2   人造石墨   LiPF6/LiBF40.9M/0.1M   EC/PC/VC27/5/3   DEC45   三甲基乙酸甲酯20 91.3 实施例10 LiCoO2 人造石墨   LiPF6/LiN(SO2CF3)20.9M/0.1M EC/PC/VC27/5/3 DEC45 三甲基乙酸甲酯20 91.6   实施例11 LiCoO2   人造石墨   LiPF61M   EC/PC/VC35/35/5   DEC20   三甲基乙酸辛酯5 90.4   比较例5 LiCoO2   人造石墨   LiPF61M   EC/PC49/49 无   辛酸甲酯 未充放电   实施例12 LiCoO2 焦炭   LiPF61M   EC/PC35/35   DEC25   三甲基乙酸辛酯5 86.5   比较例6 LiCoO2 焦炭   LiPF61M   EC/PC49/49 无   辛酸甲酯2 71.3   实施例13 LiMn2O4   人造石墨   LiBF41.2M   EC/GBL25/50   IBMC20   三甲基乙酸辛酯5 83.4   实施例14 LiMn2O4   人造石墨   LiBF41.2M   EC/GBL25/50   IBMC20   三甲基乙酸癸酯5 82.1 实施例15 LiMn2O4 人造石墨 LiBF41.2M EC/GBL25/50 IBMC20   三甲基乙酸月桂酯5 81.7   比较例7 LiMn2O4   人造石墨   LiBF41.2M   EC/GBL30/70 无 无 67.4 Table 1 positive electrode negative electrode Li salt (M) Cyclic carbonate or cyclic ester (weight %) Chain carbonate (weight%) Tertiary carboxylic acid ester or other ester (weight%) 50 cycle discharge capacity maintenance rate% Example 1 LiCoO2 artificial graphite LiPF 6 1M EC30 DEC60 Methyl trimethylacetate 10 90.7 Example 2 LiCoO2 artificial graphite LiPF 6 1M EC30 DEC50 Methyl trimethylacetate 20 91.8 Example 3 LiCoO2 artificial graphite LiPF 6 1M EC30 DEC40 Methyl trimethylacetate 30 91.4 Example 4 LiCoO2 artificial graphite LiPF 6 1M EC30 DEC30 Methyl trimethylacetate 40 85.9 Comparative example 1 LiCoO2 artificial graphite LiClO 4 1M EC50 none Methyl trimethylacetate 50 65.5 Comparative example 2 LiCoO2 artificial graphite LiCIO 4 1M PC50 none Methyl trimethylacetate 50 Not charged and discharged Comparative example 3 LiCoO2 artificial graphite LiPF 6 1M EC30 DEC70 none 81.7 Example 5 LiCoO2 artificial graphite LiPF 6 1M EC/PC30/5 DEC50 Ethyl trimethyl acetate 15 91.6 Example 6 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC27/5/3 DMC/EMC15/40 Methyl trimethylacetate 10 92.1 Example 7 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC27/5/3 DMC/IPMC15/40 Methyl trimethylacetate 10 91.9 Example 8 LiMn 2 O 4 artificial graphite LiPF 6 1M EC/PC30/5 DEC50 Methyl trimethylacetate 15 92.1 Comparative example 4 LiCoO2 artificial graphite LiPF 6 1M EC/VC15/5 DMC23 Ethyl acetate 57 81.1 Example 9 LiCoO2 artificial graphite LiPF 6 /LiBF 4 0.9M/0.1M EC/PC/VC27/5/3 DEC45 Methyl trimethylacetate 20 91.3 Example 10 LiCoO2 artificial graphite LiPF6/LiN(SO 2 CF 3 ) 2 0.9M/0.1M EC/PC/VC27/5/3 DEC45 Methyl trimethylacetate 20 91.6 Example 11 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC35/35/5 DEC20 Trimethyloctyl acetate 5 90.4 Comparative Example 5 LiCoO2 artificial graphite LiPF 6 1M EC/PC49/49 none methyl octanoate Not charged and discharged Example 12 LiCoO2 Coke LiPF 6 1M EC/PC35/35 DEC25 Trimethyloctyl acetate 5 86.5 Comparative Example 6 LiCoO2 Coke LiPF 6 1M EC/PC49/49 none Octanoic acid methyl ester 2 71.3 Example 13 LiMn 2 O 4 artificial graphite LiBF 4 1.2M EC/GBL25/50 IBMC20 Trimethyloctyl acetate 5 83.4 Example 14 LiMn 2 O 4 artificial graphite LiBF 4 1.2M EC/GBL25/50 IBMC20 Trimethyldecyl acetate 5 82.1 Example 15 LiMn 2 O 4 artificial graphite LiBF 4 1.2M EC/GBL25/50 IBMC20 Lauryl Trimethylacetate 5 81.7 Comparative Example 7 LiMn 2 O 4 artificial graphite LiBF 4 1.2M EC/GBL30/70 none none 67.4

从表1中记载的结果看到，对于正极是由含锂复合氧化物的材料形成、负极由含碳的材料形成、而且作为电解质盐使用含氟原子的锂盐的锂二次电池，将通式(I)的叔羧酸酯，特别是三甲基乙酸酯，以非水溶剂总量的35重量％以下的少量添加到由环状碳酸酯和链状碳酸酯构成的非水溶剂中的场合，可以呈现高的放电容量维持率。From the results recorded in Table 1, it can be seen that a lithium secondary battery in which the positive electrode is formed of a lithium-containing composite oxide material, the negative electrode is formed of a carbon-containing material, and a lithium salt containing a fluorine atom is used as an electrolyte salt will pass The tertiary carboxylic acid ester of formula (I), especially trimethyl acetate, is added in a small amount of 35% by weight or less of the total amount of the non-aqueous solvent to the non-aqueous solvent composed of cyclic carbonate and chain carbonate In this case, a high discharge capacity retention rate can be exhibited.

[比较例8][Comparative Example 8]

除由不含链状碳酸酯的多种环状碳酸酯配制非水溶剂(EC∶PC∶VC)使用之外，其余与实施例1同样地制作硬币电池。在测定该硬币电池的初期放电容量和50循环后的放电容量维持率时，初期放电容量，作为将上述比较例3的初期放电容量定为1时的相对值是0.45，而放电容量维持率是15.2％，该硬币电池的制作条件和电池特性示于表2中。Coin cells were produced in the same manner as in Example 1, except that a non-aqueous solvent (EC:PC:VC) was prepared from various cyclic carbonates not containing chain carbonates. When measuring the initial discharge capacity of the coin cell and the discharge capacity retention rate after 50 cycles, the initial discharge capacity was 0.45 as a relative value when the initial discharge capacity of Comparative Example 3 above was defined as 1, and the discharge capacity retention rate was 15.2%, the production conditions and battery characteristics of this coin battery are shown in Table 2.

[实施例16][Example 16]

除了配制由多种环状碳酸酯和三甲基乙酸酯构成、且不含链状碳酸酯的非水溶剂(EC∶PC∶VC∶三甲基乙酸甲酯(重量比)＝45∶45∶5∶5)使用之外，其余与实施例1同样地制作硬币电池。在测定该硬币电池的初期放电容量和50循环后的放电维持率时，初期容量，作为将上述比较例3的初期放电容量定为1时的相对值是0.91，而放电容量维持率是89.1％，该硬币电池的制作条件和电池特性示于表2中。In addition to preparing a non-aqueous solvent (EC: PC: VC: methyl trimethyl acetate (weight ratio) = 45: 45) which is composed of various cyclic carbonates and trimethyl acetates and does not contain chain carbonates. : 5: 5), a coin cell was produced in the same manner as in Example 1 except for using it. When the initial discharge capacity of the coin cell and the discharge retention rate after 50 cycles were measured, the initial capacity was 0.91 as a relative value when the initial discharge capacity of Comparative Example 3 above was set as 1, and the discharge capacity retention rate was 89.1%. , the fabrication conditions and battery characteristics of the coin cell are shown in Table 2.

[实施例17～21][Examples 17-21]

除将实施例16的非水溶剂成分中的三甲基乙酸甲酯，改换为相同含量的三甲基乙酸乙酯(实施例17)、三甲基乙酸丁酯(实施例18)、三甲基乙酸己酯(实施例19)、三甲基乙酸辛酯(实施例20)、三甲基乙酸癸酯(实施例21)、或者三甲基乙酸月桂酯(实施例22)之外，其余与实施例16同样地制作硬币电池，测定这些硬币电池的初期放电容量(将上述比较例3的初期放电容量定为1时的相对值)和50循环后的放电容量维持率。结果示于表2中。Except that the methyl trimethyl acetate in the non-aqueous solvent component of embodiment 16 is replaced with ethyl trimethyl acetate (embodiment 17), butyl trimethyl acetate (embodiment 18), trimethyl acetate of the same content Hexyl acetate (Example 19), Octyl trimethyl acetate (Example 20), Decyl trimethyl acetate (Example 21), or Lauryl trimethyl acetate (Example 22), the rest Coin batteries were produced in the same manner as in Example 16, and the initial discharge capacity (relative value when the initial discharge capacity of Comparative Example 3 above was taken as 1) and the discharge capacity retention rate after 50 cycles of these coin batteries were measured. The results are shown in Table 2.

表2 正极 负极 Li盐(M) 环状碳酸酯或环状酯(重量％) 链状碳酸酯(重量％) 叔羧酸酯或其它的酯(重量％) 初期容量   50循环放电容量维持率％   实施例16 LiCoO2   人造石墨   LiPF61M   EC/PC/VC45/45/5 无   三甲基乙酸甲酯5 0.91 89.1   实施例17 LiCoO2   人造石墨   LiPF61M   EC/PC/VC45/45/5 无   三甲基乙酸乙酯5 0.95 89.5   实施例18 LiCoO2   人造石墨   LiPF61M   EC/PC/VC45/45/5 无   三甲基乙酸丁酯5 1.00 90.4   实施例19 LiCoO2   人造石墨   LiPF61M   EC/PC/VC45/45/5 无   三甲基乙酸己酯5 1.01 90.8   实施例20 LiCoO2   人造石墨   LiPF61M   EC/PC/VC45/45/5 无   三甲基乙酸辛酯5 1.00 90.5   实施例21 LiCoO2   人造石墨   LiPF61M   EC/PC/VC45/45/5 无   三甲基乙酸癸酯5 1.00 90.4   实施例22 LiCoO2   人造石墨   LiPF61M   EC/PC/VC45/45/5 无   三甲基乙酸月桂酯5 0.99 90.1   比较例8 LiCoO2   人造石墨   LiPF61M   EC/PC/VC47.5/47.5/5 无 无 0.45 15.2 Table 2 positive electrode negative electrode Li salt (M) Cyclic carbonate or cyclic ester (weight %) Chain carbonate (weight%) Tertiary carboxylic acid ester or other ester (weight%) initial capacity 50 cycle discharge capacity maintenance rate% Example 16 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC45/45/5 none Methyl trimethylacetate 5 0.91 89.1 Example 17 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC45/45/5 none Ethyl trimethylacetate 5 0.95 89.5 Example 18 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC45/45/5 none Butyl trimethyl acetate 5 1.00 90.4 Example 19 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC45/45/5 none trimethylhexyl acetate 5 1.01 90.8 Example 20 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC45/45/5 none Trimethyloctyl acetate 5 1.00 90.5 Example 21 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC45/45/5 none Trimethyldecyl acetate 5 1.00 90.4 Example 22 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC45/45/5 none Lauryl Trimethylacetate 5 0.99 90.1 Comparative Example 8 LiCoO2 artificial graphite LiPF 6 1M EC/PC/VC47.5/47.5/5 none none 0.45 15.2

从表2中记载的测定结果看到，对于正极由含锂复合氧化物的材料形成、负极由含碳的材料形成、而且作为电解质盐使用含氟原子的锂盐的锂二次电池，通式(I)的叔羧酸酯，特别是三甲基乙酸酯，以占非水溶剂总量的35重量％以下的少量添加到由环状碳酸酯构成的非水溶剂中的场合，可呈现高的放电容量维持率。再者，由于非水溶剂中不添加链状碳酸酯，通常，初期放电容量大大地降低(比较例8)，但是通过少量添加通式(I)的叔羧酸酯，特别是三甲基乙酸酯来代替链状碳酸酯，初期放电容量的下降会显著地减少，另一方面看到，实现了放电容量维持率明显的提高。From the measurement results recorded in Table 2, it can be seen that for a lithium secondary battery in which the positive electrode is formed of a lithium-containing composite oxide material, the negative electrode is formed of a carbon-containing material, and a lithium salt containing a fluorine atom is used as an electrolyte salt, the general formula (I) tertiary carboxylic acid ester, especially trimethyl acetate, when added to a non-aqueous solvent composed of cyclic carbonate in a small amount of 35% by weight or less of the total non-aqueous solvent, can exhibit High discharge capacity retention rate. Furthermore, since no chain carbonate is added in the non-aqueous solvent, usually, the initial discharge capacity is greatly reduced (comparative example 8), but by adding a small amount of tertiary carboxylic acid ester of general formula (I), especially trimethylethane Ester instead of chain carbonate, the decline in initial discharge capacity will be significantly reduced, on the other hand, it can be seen that the discharge capacity maintenance rate has been significantly improved.

进一步还弄清楚了，通式(I)的叔羧酸酯中的醇残基(R4)是碳原子数4以上的烷基的场合，初期放电容量，与添加链状碳酸酯的场合成为同等水平，另外还呈现高的放电容量维持率。Furthermore, it became clear that when the alcohol residue (R 4 ) in the tertiary carboxylic acid ester of the general formula (I) is an alkyl group having 4 or more carbon atoms, the initial discharge capacity becomes equal to that of the case where a chain carbonate is added. At the same level, it also exhibits a high discharge capacity retention rate.

[实施例22][Example 22]

用下述方法评价电解液向用于锂二次电池的多微孔性隔板的孔部的浸透性。The permeability of the electrolytic solution to the pores of the microporous separator used for lithium secondary batteries was evaluated by the following method.

往1M的LiPF6/PC的电解质溶液中，添加相对于电解质溶液100重量份为2重量份或4重量份的量的三甲基乙酸酯，配制电解液。在该电解液中，将由聚丙烯制多微孔膜构成的隔板(商标名：セルガ-ド#2500、CELGARD Inc.制)浸渍20秒钟，然后取出，通过目视评价隔板的透光性。其结果示于表3中。To an electrolytic solution of 1M LiPF 6 /PC, trimethyl acetate was added in an amount of 2 parts by weight or 4 parts by weight based on 100 parts by weight of the electrolytic solution to prepare an electrolytic solution. In this electrolytic solution, a separator made of a polypropylene microporous film (trade name: Selga-do #2500, manufactured by CELGARD Inc.) was immersed for 20 seconds, then taken out, and the light transmission of the separator was visually evaluated. sex. The results are shown in Table 3.

表3   添加量   三甲基乙酸乙酯   三甲基乙酸丁酯   三甲基乙酸己酯   三甲基乙酸辛酯   三甲基乙酸月桂酯   2份4份   不透明半透明   半透明大致透明   大致透明完全透明   完全透明完全透明   完全透明完全透明 table 3 Amount added ethyl trimethyl acetate Butyl trimethylacetate trimethylhexyl acetate octyl trimethylacetate Lauryl trimethylacetate 2 servings 4 servings opaque translucent translucent almost transparent roughly transparent completely transparent completely transparent completely transparent completely transparent completely transparent

从表3的结果了解到，醇残基的烷基的碳原子数4以上的三甲基乙酸酯，对隔板的亲和性，比醇残基的烷基的碳原子数2的三甲基乙酸酯高，因此，在与多微孔隔板接触情况下放置时，迅速地浸透到隔板的多孔结构中。这一点，关系到锂二次电池的制造工序的制造时间的缩短。即，在锂二次电池的制造工序中，将正极板、隔板、负极板构成的叠层体装到电池容器内之后，填充电解液，然后进行安装电池容器盖的操作，但是该盖的安装，必须在填充了的电解液置换掉隔板的多微孔结构内存在的空气，并充满该多微孔结构内之后进行实施。因此，通过使用在短时间内浸透到隔板的多微孔结构中的电解液，即可实现缩短锂二次电池的制造时间。From the results in Table 3, it was found that trimethyl acetate having an alkyl group of an alcohol residue having 4 or more carbon atoms has a higher affinity for the separator than trimethyl acetate having an alkyl group of an alcohol residue having 2 carbon atoms. Methyl acetate is high and, therefore, when left in contact with a microporous separator, rapidly permeates into the porous structure of the separator. This point leads to shortening of the manufacturing time in the manufacturing process of the lithium secondary battery. That is, in the manufacturing process of a lithium secondary battery, after a laminated body consisting of a positive electrode plate, a separator, and a negative electrode plate is installed in a battery container, the electrolyte solution is filled, and then the operation of installing the battery container cover is carried out. Installation must be carried out after the filled electrolyte replaces the air existing in the microporous structure of the separator and fills the microporous structure. Therefore, shortening the manufacturing time of the lithium secondary battery can be achieved by using an electrolytic solution that permeates into the microporous structure of the separator in a short time.

再者，本发明并不限于所记载的实施例，从发明的宗旨可容易类推的各种组合都是可能的，特别是，上述实施例的溶剂的组合并不被限定。另外，上述实施例是关于硬币电池的，但是本发明也适用于圆筒形、棱柱形的电池和叠层形的聚合物电池。Furthermore, the present invention is not limited to the described examples, and various combinations that can be easily deduced from the gist of the invention are possible. In particular, the combination of solvents in the above-mentioned examples is not limited. In addition, the above-mentioned embodiments are related to coin batteries, but the present invention is also applicable to cylindrical, prismatic batteries and laminated polymer batteries.

[工业适用性][Industrial Applicability]

在锂二次电池的制造时，通过使用本发明的非水电解液，能够提供，电池的循环特性、电容、以及充电保存特性等的电池特性优良的、并可抑制高温使用时的电池膨胀的锂二次电池。In the manufacture of lithium secondary batteries, by using the non-aqueous electrolytic solution of the present invention, it is possible to provide a battery that is excellent in battery characteristics such as cycle characteristics, capacity, and charge storage characteristics, and that can suppress battery expansion when used at a high temperature. Lithium secondary battery.

Claims (15)

1. lithium secondary battery, it is characterized in that, negative pole, dividing plate and the electrolytic salt that this battery is the positive pole that is equipped with the material by lithium-contained composite oxide to constitute, be made of material containing carbon is dissolved in the lithium secondary battery of the nonaqueous electrolytic solution that nonaqueous solvents forms, this electrolytic salt is the lithium salts with fluorine atom, this nonaqueous solvents contains cyclic carbonate, and contains the following general formula of usefulness (I) of 0.5～35 weight % content in this nonaqueous solvents:
The t-carboxylic acid esters of expression, wherein, R 1, R 2, and R 3, represent methyl, ethyl, fluorine atom or chlorine atom respectively independently, and R 4The alkyl of expression carbon number 1～20.
2. according to the lithium secondary battery of claim 1 record, wherein, electrolytic salt is to be selected from LiPF 6, LiBF 4, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2, LiC (SO 2CF 3) 3, LiPF 4(CF 3) 2, LiPF 3(C 2F 5) 3, LiPF 3(CF 3) 3, LiPF 3(iso-C 3F 7) 3And LiPF 5(iso-C 3F 7) salt.
3. according to the lithium secondary battery of claim 1 record, wherein, the content of the cyclic carbonate in the nonaqueous solvents is in the scope of 10～80 weight %.
4. according to the lithium secondary battery of claim 1 record, wherein, cyclic carbonate is the compound that is selected from ethylene carbonate, propylene carbonate, butylene carbonate and carbonic acid ethenylidene ester.
5. according to the lithium secondary battery of claim 1 record, wherein, also contain the linear carbonate of 80 weight % in the nonaqueous solvents with interior amount.
6. according to the lithium secondary battery of claim 1 record, wherein, the content of the t-carboxylic acid esters in the nonaqueous solvents is in the scope of 1～20 weight %.
7. according to the lithium secondary battery of claim 1 record, wherein, negative pole is made of natural or artificial graphite.
8. according to the lithium secondary battery of claim 1 record, wherein, in general formula (I), R 4It is the alkyl of carbon number 4～20.
9. secondary lithium batteries nonaqueous electrolytic solution, it is characterized in that, this electrolyte is, contains the nonaqueous electrolytic solution that the lithium salts of fluorine atom forms in containing the nonaqueous solvents of cyclic carbonate as dissolving electrolyte salt, and this nonaqueous solvents also contains the following general formula of usefulness (I) of 0.5～35 weight % content:
The t-carboxylic acid esters of expression, wherein, R 1, R 2, R 3Represent methyl, ethyl, fluorine atom or chlorine atom respectively independently, and R 4The alkyl of expression carbon number 1～20.
10. according to the nonaqueous electrolytic solution of claim 9 record, wherein, electrolytic salt is to be selected from LiPF 6, LiBF 4, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2, LiC (SO 2CF 3) 3, LiPF 4(CF 3) 2, LiPF 3(C 2F 5) 3, LiPF 3(CF 3) 3, LiPF 3(iso-C 3F 7) 3And LiPF 5(iso-C 3F 7) salt.
11. according to the nonaqueous electrolytic solution of claim 9 record, wherein, the content of the cyclic carbonate in the nonaqueous solvents is in the scope of 10～80 weight %.
12. according to the nonaqueous electrolytic solution of claim 9 record, wherein, cyclic carbonate is the compound that is selected from ethylene carbonate, propylene carbonate, butylene carbonate and carbonic acid ethenylidene ester.
13. the nonaqueous electrolytic solution according to claim 9 record wherein, also contains the linear carbonate of 80 weight % with interior amount in the nonaqueous solvents.
14. according to the nonaqueous electrolytic solution of claim 9 record, wherein, the content of the t-carboxylic acid esters in the nonaqueous solvents is in the scope of 1～20 weight %.
15. according to the nonaqueous electrolytic solution of claim 9 record, wherein, in general formula (I), R 4It is the alkyl of carbon number 4～20.
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